JPWO2007018028A1 - Thin glass laminate and method for manufacturing display device using thin glass laminate - Google Patents

Abstract

A thin glass substrate and a supporting glass substrate, which suppresses the occurrence of convex defects due to mixing of air bubbles and foreign matters, is easy to separate the thin glass substrate and the supporting glass substrate, and has excellent heat resistance, and A method for producing a display device using the thin glass laminate and a silicone for release paper for the thin glass laminate are provided. A thin glass laminate obtained by laminating a thin glass substrate and a supporting glass substrate, wherein the thin glass substrate and the supporting glass substrate are provided with an easily peelable and non-adhesive silicone resin layer. A thin glass laminate characterized by being laminated.

Description

  The present invention relates to a glass substrate used in a display device such as a liquid crystal display or an organic EL display, and more specifically, the thin glass substrate and support used in manufacturing a display device using a thin glass substrate. The present invention relates to a laminate with a glass substrate, a method for producing a display device using the laminate, and silicone for release paper for the thin glass laminate.

In the field of liquid crystal display devices (LCD), organic EL display devices (OLED), especially portable display devices such as mobile phones and mobile phones, weight reduction and thinning of display devices are important issues.
In order to cope with this problem, studies have been made to further reduce the thickness of the glass substrate used in the display device. However, if the thickness of the glass substrate is reduced, a decrease in strength becomes a problem and the amount of deflection is large. As it is, it cannot be applied to the current production line.
Therefore, in order to reinforce the strength of the thin glass substrate (hereinafter referred to as “thin glass substrate”) and to secure the plate thickness applicable to the current production line, the thin glass substrate is supported by other supports. By performing a predetermined process for manufacturing a display device in a state of being laminated with a glass substrate to form a laminate (thin glass laminate), and separating the thin glass substrate and the supporting glass substrate after the completion of the process A method of manufacturing a display device has been proposed (see Patent Documents 1 to 6).

  In the method of manufacturing these display devices, as a method of laminating and fixing a thin glass substrate and a supporting glass substrate, a method of fixing both using electrostatic adsorption force or vacuum adsorption force generated between glass substrates ( For example, refer to Patent Document 1), a method of fixing both ends of a glass substrate using a glass frit (for example, refer to Patent Document 2), and irradiating a laser beam near the end face of the peripheral portion to fuse two glass substrates. A method (for example, see Patent Document 3), or a method in which a removable pressure-sensitive adhesive or pressure-sensitive adhesive sheet is disposed over the entire surface between glass substrates, and both are fixed by the adhesive force (for example, see Patent Documents 4 to 6). Proposed.

These methods have potential problems that can adversely affect the display device being manufactured.
That is, a method in which glass substrates are fixed to each other with an electrostatic adsorption force or a vacuum adsorption force, a method in which both ends of the glass substrate are fixed with glass frit, or a laser beam is irradiated to the vicinity of the end surface of the peripheral portion. In the method of fusing together glass substrates, it is difficult to avoid the inclusion of bubbles and convex defects that include foreign matters such as dust in the process of laminating and adhering the glass substrates without any intermediate layer. It is difficult to obtain a glass substrate laminate having a smooth surface.
In the case of a method in which a removable adhesive or pressure sensitive adhesive sheet is placed over the entire surface between glass substrates, it is easier to avoid mixing of bubbles than in the case of directly laminating glass, and convex defects due to foreign matter. It is thought that there is little occurrence of. However, it becomes difficult to separate the thin glass substrate and the supporting glass substrate, and the thin glass substrate may be damaged during the separation. Further, the remaining adhesive on the thin glass substrate after separation also becomes a problem. Furthermore, since the manufacturing process of the display device includes a process that requires processing at a high temperature, such as the firing process of the insulating film and the alignment film in the manufacturing process of the liquid crystal display device, the adhesive and the adhesive sheet However, a method for achieving both heat resistance and removability has not been proposed.

JP 2000-241804 A JP 58-54316 A JP 2003-2160868 A Japanese Patent Laid-Open No. 8-86993 Japanese Patent Laid-Open No. 9-105896 JP 2000-252342 A

  In order to solve the above-mentioned problems of the prior art, the present invention suppresses the occurrence of convex defects due to the mixing of bubbles and foreign matter between the thin glass substrate and the supporting glass substrate, and the separation of the thin glass substrate and the supporting glass substrate is achieved. An object of the present invention is to provide a thin glass laminate that is easy and excellent in heat resistance, a method for producing a display device using the thin glass laminate, and a release paper silicone for the thin glass laminate. And

In order to achieve the above object, the present invention is a thin glass laminate obtained by laminating a thin glass substrate and a supporting glass substrate,
Provided is a thin glass laminate in which the thin glass substrate and the supporting glass substrate are laminated via a silicone resin layer having easy peelability and non-adhesiveness.
The silicone resin layer having easy peelability and non-adhesiveness preferably further has low silicone migration.

Moreover, it is preferable that the said silicone resin layer which has easy peelability and non-adhesiveness is a layer which consists of a hardened | cured material of release paper silicone.
The cured product of the release paper silicone is a cross-linked reaction product of a linear polyorganosiloxane having vinyl groups at both ends and / or side chains and a methylhydrogen polysiloxane having a hydrosilyl group in the molecule. Preferably there is.

Hereinafter, in the present specification, a thin glass laminate in which a thin glass substrate and a supporting glass substrate are laminated via an easily peelable and non-adhesive silicone resin layer is referred to as “thin glass of the present invention. It is called “laminated body”.
In the thin glass laminate of the present invention, the thickness of the thin glass substrate is less than 0.3 mm, and the total thickness of the support glass substrate and the easily peelable and non-adhesive silicone resin layer is 0. It is preferably 5 mm or more.
In the thin glass laminate of the present invention, the difference between the linear expansion coefficient of the supporting glass substrate and the linear expansion coefficient of the thin glass substrate is preferably 15 × 10 ⁻⁷ / ° C. or less.

Further, the present invention is a method for manufacturing a display device using a thin glass substrate,
Forming a silicone resin layer having easy peelability and non-adhesiveness on a supporting glass substrate;
Laminating a thin glass substrate on the silicone resin layer forming surface of the support glass substrate;
Performing a predetermined process for manufacturing a display device on the thin glass substrate;
Separating the processed thin glass substrate and the supporting glass substrate, and a method of manufacturing a display device using a thin glass laminate (hereinafter referred to as “display device manufacturing method of the present invention”). ").

In the method for manufacturing a display device of the present invention, the silicone resin layer having easy peelability and non-adhesiveness is preferably a layer made of a cured product of silicone for release paper.
The cured product of the release paper silicone is a cross-linked reaction product of a linear polyorganosiloxane having vinyl groups at both ends and / or side chains and a methylhydrogen polysiloxane having a hydrosilyl group in the molecule. Preferably there is.

In the method for producing a display device of the present invention, the step of forming a silicone resin layer having easy peelability and non-adhesiveness on a supporting glass substrate comprises applying release paper silicone on the supporting glass substrate, and thereafter It preferably includes curing the release paper silicone.
It is preferable that the release paper silicone is substantially free of non-reactive silicone.
The release paper silicone preferably contains a linear polyorganosiloxane having vinyl groups at both ends and / or side chains, a methylhydrogen polysiloxane having a hydrosilyl group in the molecule, and a platinum catalyst. .
The release paper silicone coating is preferably performed using a die coating method, a spin coating method, or a screen printing method.
The release paper silicone is preferably heat-cured at a temperature of 50 to 250 ° C.
The step of laminating the thin glass substrate on the surface of the support glass substrate on which the silicone resin layer is formed is preferably performed using a vacuum press or a vacuum laminate.
Moreover, this invention provides the silicone for release paper for thin glass laminated bodies used for lamination | stacking of a thin glass substrate and a support glass substrate.

In the thin glass laminate of the present invention, since the thin glass substrate and the supporting glass substrate are laminated through a flexible silicone resin layer, bubbles are hardly mixed at the time of lamination, and even when bubbles are mixed, There is an advantage that the bubbles can be easily removed by pressure bonding using a roll or a press. In particular, when the lamination of the thin glass substrate and the supporting glass substrate is performed using a vacuum laminating method or a vacuum pressing method, mixing of bubbles is suppressed and adhesion is also good. In addition, when laminating the thin glass substrate and the supporting glass substrate using the vacuum laminating method or the vacuum press method, even if minute bubbles remain, the bubbles do not grow by heating, and the thin glass substrate There is also an advantage that it is difficult to lead to a convex defect.
In addition, even when foreign matter such as dust is mixed into the laminated interface, there is an advantage that the flexible silicone resin layer is deformed and is not easily connected to the convex defect of the thin glass laminate.
Moreover, since the layer interposed between the thin glass substrate and the supporting glass substrate is a silicone resin layer having excellent heat resistance, the heat resistance is also good.

  In the thin glass laminate of the present invention, since the thin glass substrate and the supporting glass substrate are laminated via a silicone resin layer having easy peelability and non-adhesiveness, the thin glass substrate and the supporting glass substrate can be easily provided. It is possible to separate the thin glass substrates from each other when the glass substrates are separated from each other. This property is also exhibited even after the thin glass laminate is heated in the atmosphere at a temperature of 300 ° C. for 1 hour. Therefore, it is suitable for use in a manufacturing process of a display device that involves heat treatment.

  Moreover, if the silicone resin layer has low silicone migration, the components in the silicone resin layer are unlikely to migrate to the thin glass substrate when the glass substrates are separated from each other. Therefore, after separation, the supporting glass substrate on which the silicone resin layer is formed can be used repeatedly for lamination with other thin glass substrates. In addition, since components in the silicone resin layer are unlikely to migrate to the surface of the thin glass substrate after separation, there is no possibility of poor attachment or the like when a polarizing plate or the like is attached to the surface of the thin glass substrate.

The display device manufacturing method of the present invention uses the thin glass laminate of the present invention to prevent deflection of the thin glass substrate and damage of the thin glass substrate during manufacturing. The yield can be improved.
In the method for manufacturing a display device of the present invention, when the step of laminating the thin glass substrate on the silicone resin layer forming surface of the support glass substrate is performed using a vacuum press or vacuum lamination, bubbles are mixed into the silicone resin layer. Can be suppressed. As a result, in the step of forming a transparent electrode such as ITO under vacuum, there is an advantage that the generation of defects starting from bubbles mixed in the silicone resin layer can be suppressed.

It is a cross-sectional schematic diagram of the thin glass laminated body of this invention. It is a cross-sectional schematic diagram of the thin glass laminated body explaining the peeling test (1) of this invention. It is a cross-sectional schematic diagram of the thin glass laminated body explaining the shear strength test of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 40: Support glass substrate 2, 50: Thin glass substrate 3, 60: Resin layer 10, A: Thin glass laminated body 20, 25, 30: Polycarbonate

Hereinafter, the thin glass laminated body of this invention is demonstrated.
The thin glass laminated body 10 of this invention has a structure which has the silicone resin layer 3 between the support glass substrate 1 and the thin glass substrate 2 as shown in FIG.
The thin glass substrate is a glass substrate for a display device such as an LCD or an OLED, and has a thickness of less than 0.3 mm. The thickness of the thin glass substrate is preferably 0.2 mm or less, and more preferably 0.1 mm or less. The thickness of the thin glass substrate is preferably 0.05 mm or more.
The display device targeted by the present invention is a small display device mainly used for mobile terminals such as mobile phones and PDAs. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, and an MIM type.

Properties required for a thin glass substrate such as heat shrinkage, surface shape, chemical resistance, and the like vary depending on the type of display device. Therefore, the thin glass substrate may be made of alkali glass. However, alkali-free glass is preferred as the thin glass substrate because of its low thermal shrinkage.
In the present invention, the thin glass substrate preferably has a low thermal shrinkage rate. In the case of glass, a linear expansion coefficient defined in JIS R3102 (1995) is used as an index of thermal expansion and contraction. The thin glass substrate preferably has a linear expansion coefficient of 50 × 10 ⁻⁷ / ° C. or lower, more preferably 45 × 10 ⁻⁷ / ° C. or lower, and further 40 × 10 ⁻⁷ / ° C. or lower. Preferably, it is more preferably 30 × 10 ⁻⁷ / ° C. or less, and most preferably 20 × 10 ⁻⁷ / ° C. or less.

Since the supporting glass substrate is laminated with the thin glass substrate for the purpose of reinforcing the strength of the thin glass substrate, the supporting glass substrate needs to be thicker than the thin glass substrate. The thickness of the supporting glass substrate is preferably such that the laminate with the thin glass substrate can be flowed in the current production line. For example, when the current production line is designed to flow a substrate having a thickness of 0.5 mm and the thickness of the thin glass substrate is 0.1 mm, the thickness of the supporting glass substrate is easy. The thickness of the silicone resin layer having peelability and non-adhesiveness is preferably 0.4 mm. As described above, the thickness of the thin glass substrate is preferably 0.2 mm or less. The current production line is most commonly designed to flow a glass substrate having a thickness of 0.7 mm. For this reason, it is preferable that the total thickness of the supporting glass substrate and the easily peelable and non-adhesive silicone resin layer is 0.5 mm or more. However, the production line is not limited to those designed to flow a glass substrate having a thickness of 0.5 mm or 0.7 mm, and is designed to flow a glass substrate having a thickness other than these. In some cases. For example, it may be designed to flow a glass substrate having a thickness of less than 0.5 mm, or may be designed to flow a glass substrate having a thickness of more than 0.7 mm.
Considering the thickness of the silicone resin layer having easy peelability and non-adhesiveness described later, the thickness of the supporting glass substrate is preferably 0.3 to 0.8 mm. The total thickness of the supporting glass substrate and the easily peelable and non-adhesive silicone resin layer is preferably 0.5 mm or more, and more preferably 1.0 mm or less.

  Further, since the supporting glass substrate reinforces the strength of the thin glass substrate, the material thereof is not particularly limited and may be either alkali glass or non-alkali glass. However, it is preferable that the support glass substrate has substantially the same linear expansion coefficient as that of the thin glass substrate. When the linear expansion coefficient of the support glass substrate is larger than the linear expansion coefficient of the thin glass substrate, since the expansion of the support glass substrate is suppressed by the thin glass laminate in the heating process of the display device manufacturing process, the thin glass laminate If the body is warped and the linear expansion coefficient of the supporting glass substrate is smaller than the linear expansion coefficient of the thin glass substrate, the thin glass substrate peels off from the silicone resin layer due to the expansion of the thin glass substrate. This is because inconvenience occurs.

In the present invention, when the linear expansion coefficient is substantially the same, it does not mean that the linear expansion coefficient of the thin glass substrate and the linear expansion coefficient of the supporting glass substrate completely match, There may be a difference. The difference in coefficient of linear expansion between the thin glass substrate and the supporting glass substrate is preferably 35 × 10 ⁻⁷ / ° C. or less, more preferably 25 × 10 ⁻⁷ / ° C. or less, and even more preferably 15 × 10 ^{− 7} / ° C or less.

  The supporting glass substrate reinforces the thin glass substrate and, when the thin glass laminate moves on the production line, serves as a base for holding the thin glass substrate, so the size thereof is the size of the thin glass substrate. Is preferably equal to or greater than.

When producing the thin glass laminate of the present invention, a silicone resin layer having easy peelability and non-adhesiveness is formed on a supporting glass substrate, and then the thin glass substrate is formed on the silicone resin layer forming surface of the supporting glass substrate. Laminate.
The easily peelable and non-adhesive silicone resin layer is a silicone resin layer having appropriate flexibility, and is not very close to the thin glass substrate by adhesive force like an adhesive. In this case, the thin glass substrate is fixed by a force caused by van der Waals force between opposing solid molecules, that is, an adhesion force. Specific embodiments of the silicone resin layer having easy peelability and non-adhesiveness will be described later.

The easily peelable and non-adhesive silicone resin layer fixes the thin glass substrate by adhesion, so the force to shift the thin glass substrate and the supporting glass substrate parallel to the lamination interface, that is, the shearing force is high. Indicates the value. For this reason, a thin glass substrate does not shift | deviate from a support glass substrate during the manufacturing process of a display apparatus. Therefore, there is no possibility that the substrates are separated from each other due to the deviation. The shear force is a load when the supporting glass substrate is peeled off without breaking the glass substrate in the shear strength test described later in that the thin glass substrate does not deviate from the supporting glass substrate during the manufacturing process of the display device. Is preferably 0.1 kg weight / cm ² or more, more preferably 0.5 kg weight / cm ² or more, and even more preferably 1 kg weight / cm ² or more.
On the other hand, due to the easy peelability and non-adhesiveness of the silicone resin layer, the force for pulling the thin glass substrate away from the supporting glass substrate in the vertical direction, that is, the peel force is remarkably low. For this reason, it is possible to easily separate the supporting glass substrate from the thin glass substrate after performing a predetermined process for manufacturing the display device on the thin glass substrate.
The peeling force means that the supporting glass substrate can be easily separated from the thin glass substrate. In the peeling test (1) described later, the load at which the supporting glass substrate peels without breaking the glass substrate is 2 kg. / cm ² or less, particularly 1.5kg weight / cm ² or less, further 1kg weight / cm ² or less, preferably 0.5kg weight / cm ² or less. When a flexible substrate capable of roll-to-roll such as a resin plate is used as a support substrate, the peel force should be evaluated by an angle peel test such as a 90 ° peel test or a 180 ° peel test. . However, in a peel test between glass substrates having a certain degree of rigidity, it is necessary to evaluate the peel force by a test method such as a peel test (1) (so-called 0 ° peel test). Therefore, even when the peeling force is evaluated, it is preferable to be in the above range by a test method such as the peel test (1).
Since the silicone resin layer is excellent in heat resistance, after the heat treatment, for example, after heating for 1 hour at a temperature of 300 ° C. in the atmosphere, the above-mentioned characteristics are exhibited in that the shearing force is high but the peeling force is extremely low. be able to. Hereinafter, in the present specification, after the heat treatment, for example, the silicone resin layer after heating for 1 hour at a temperature of 300 ° C. in the atmosphere has the above characteristics, that is, the shearing force is high, but the peeling force is extremely low. Is said to be “excellent in peelability after heat treatment”.

  The easily peelable and non-adhesive silicone resin layer has moderate flexibility, so that it is difficult for bubbles to be mixed during lamination, and even when bubbles are mixed, it can be crimped using a roll or press, The bubbles can be easily removed. Further, even when foreign matter such as dust is mixed into the laminated interface, the silicone resin layer having flexibility is deformed, so that it is difficult to form a convex defect of the thin glass laminate.

The silicone resin layer having easy peelability and non-adhesiveness is preferably a cured product of silicone for release paper. The silicone for release paper is mainly composed of silicone containing linear dimethylpolysiloxane with excellent releasability in the molecule. The silicone for release paper contains the above-mentioned main agent and a crosslinking agent, and is fixed to the substrate surface by curing using a catalyst, a photopolymerization initiator, or the like. A cured product (cured coating film) of silicone for release paper has excellent releasability and moderate flexibility.
Moreover, the surface energy of the silicone resin layer having easy peelability and non-adhesiveness is 16 to 16 because it is easy to remove air bubbles mixed during lamination and the support glass substrate can be easily separated from the thin glass substrate. It is preferably 21 erg / cm ² .
If silicone for release paper having such characteristics is used as the silicone resin layer, a silicone resin layer having appropriate flexibility and having easy peeling and non-adhesiveness can be obtained. Whether or not the release layer contains silicone for release paper can be estimated to some extent from IR (infrared spectroscopy) and the strength and adhesiveness of the resin layer.

  The silicone for release paper is classified into a condensation reaction type silicone, an addition reaction type silicone, an ultraviolet ray curable type silicone, and an electron beam curable type silicone according to its curing mechanism. Any of these can be used in the present invention. However, among these, it is easy to form a curing reaction, it is easy to form a silicone resin layer having easy peelability and non-adhesiveness when a cured film is formed, and an addition reaction type silicone is used from the viewpoint of excellent heat resistance of a cured product. Most preferred.

分子内にハイドロシリル基を有するメチルハイドロジェンポリシロキサンは、下記式で表される化合物であり、式中のａは整数を表し、ｂは１以上の整数を表す。

なお、メチルハイドロジェンポリシロキサンの末端のメチル基の一部は水素原子や水酸基であってもよい。
両末端及び／又は側鎖中にビニル基を有する直鎖状ポリオルガノシロキサンからなる主剤と、分子内にハイドロシリル基を有するメチルハイドロジェンポリシロキサンからなる架橋剤の混合比率においては、ハイドロシリル基とビニル基のモル比が１．３／１〜０．７／１となるように混合比率を調整することが好ましい。特には、１．２／１〜０．８／１となるように混合比率を調整することが好ましい。
ハイドロシリル基とビニル基のモル比が１．３／１を超える場合には、加熱処理後の剥離力が上昇し、剥離性が十分でない可能性がある。特にＬＣＤなどを製造する場合には、加熱処理後に支持ガラス基板を剥離する場合が多く、加熱処理後の剥離性は大きな問題となる。又、ハイドロシリル基とビニル基のモル比が０．７／１未満である場合には、硬化物の架橋密度が低下するため、耐薬品性等に問題が生じる可能性がある。ハイドロシリル基とビニル基のモル比が１．３／１を超える場合に、加熱処理後の剥離力が上昇する原因は明らかではないが、加熱処理により、硬化物中の未反応のハイドロシリル基とガラス表面のシラノール基とのなんらかの反応が関与しているものと考えている。The addition reaction type silicone includes a main agent composed of a linear polyorganosiloxane having vinyl groups at both ends and / or side chains, and a cross-linking agent composed of a methylhydrogen polysiloxane having a hydrosilyl group in the molecule. The heat curing reaction is performed in the presence of a platinum-based catalyst.
The linear polyorganosiloxane having vinyl groups at both ends and / or side chains is a compound represented by the following [Chemical Formula 1] and [Chemical Formula 2]. [Chemical Formula 1] m and n in the formula represent an integer and may be 0. When m is 0, a linear polyorganosiloxane having vinyl groups at both ends is obtained. When m is an integer of 1 or more, it becomes a linear polyorganosiloxane having vinyl groups at both ends and side chains. In the formula [2], m represents an integer of 2 or more, n represents an integer, and may be 0. In this case, a linear polyorganosiloxane having a vinyl group in the side chain is obtained.

The methyl hydrogen polysiloxane having a hydrosilyl group in the molecule is a compound represented by the following formula, in which a represents an integer and b represents an integer of 1 or more.

A part of the methyl group at the terminal of the methyl hydrogen polysiloxane may be a hydrogen atom or a hydroxyl group.
In the mixing ratio of the main agent composed of linear polyorganosiloxane having vinyl groups at both ends and / or side chains and the cross-linking agent composed of methylhydrogen polysiloxane having hydrosilyl groups in the molecule, hydrosilyl groups It is preferable to adjust the mixing ratio so that the molar ratio of vinyl group to 1.3 / 1 to 0.7 / 1. In particular, the mixing ratio is preferably adjusted to be 1.2 / 1 to 0.8 / 1.
When the molar ratio of the hydrosilyl group and the vinyl group exceeds 1.3 / 1, the peeling force after the heat treatment is increased, and the peelability may not be sufficient. In particular, when manufacturing an LCD or the like, the support glass substrate is often peeled after the heat treatment, and the peelability after the heat treatment becomes a big problem. Further, when the molar ratio of hydrosilyl group to vinyl group is less than 0.7 / 1, the crosslink density of the cured product is lowered, which may cause a problem in chemical resistance. When the molar ratio of hydrosilyl group to vinyl group exceeds 1.3 / 1, it is not clear why the peel strength after the heat treatment is increased, but the heat treatment causes unreacted hydrosilyl groups in the cured product. It is thought that some kind of reaction with the silanol group on the glass surface is involved.

A platinum-based catalyst is preferably used as the catalyst used in the heat curing reaction, and a known catalyst can be used as the platinum-based catalyst. Specific examples include chloroplatinic acid such as chloroplatinic acid and dichloroplatinic acid, alcohol compounds of chloroplatinic acid, aldehyde compounds, or chain salts of chloroplatinic acid and various olefins.
The platinum-based catalyst is preferably used in an amount of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the release paper silicone.

  There are three types of silicone for release paper: solvent type, emulsion type, and solventless type, and any type can be used. However, the solventless type is preferable in terms of productivity, safety, and environmental characteristics. When the solventless type is used, bubbles do not easily remain in the resin layer because it does not contain a solvent that causes foaming during curing, that is, heat curing, ultraviolet curing, or electron beam curing.

  The silicone resin layer having easy peelability and non-adhesiveness may be formed using only one type of release paper silicone, but may be formed using two or more types of release paper silicone. When it is formed using two or more types of release paper silicones, it may be a multi-layered silicone resin layer in which two or more types of release paper silicones are laminated together, or two types in one layer. It may be a mixed silicone resin layer containing the above release paper silicone.

The easily peelable and non-adhesive silicone resin layer preferably has a low silicone migration property because when the glass substrates are separated from each other, the components in the silicone resin layer hardly migrate to the thin glass substrate. .
The ease of migration of the components in the silicone resin layer can be determined using the residual adhesion rate of the silicone resin layer as an index. The residual adhesion rate of the silicone resin layer can be measured by the following method.
Method for measuring residual adhesion rate A standard adhesive tape of 15 mm width (Cellotape CT405A-15 (manufactured by Nichiban Co., Ltd.)) is pressure-bonded to the surface of the silicone resin layer with the help of human hands, and heated in the atmosphere at 70 ° C. for 20 hours. . After 20 hours, the standard adhesive tape is peeled off from the silicone resin layer. After the peeled standard adhesive tape is bonded to the surface of a clean glass substrate (for example, AN100 (Asahi Glass Co., Ltd.)), 180 ° peel strength (300 mm / min) is measured (peel strength (A)).
The same standard adhesive tape as described above was pressure-bonded to the surface of a clean glass substrate (for example, AN100) with the help of human hands, and then allowed to stand in a room temperature atmosphere for 20 hours. After 20 hours, the standard adhesive tape is peeled off from the glass substrate surface. After the peeled standard adhesive tape is bonded to the surface of a glass substrate (for example, AN100), 180 ° peel strength (300 mm / min) is measured (peel strength (B)).
The residual adhesion rate is obtained by the following formula.
Residual adhesion rate (%) = peel strength (A) / peel strength (B) × 100

  The silicone resin layer having easy peelability and non-adhesiveness preferably has a residual adhesion ratio determined by the above-described measurement method of 95% or more, and more preferably 98% or more. If the residual adhesion rate is 95% or more, it is considered that the migration of components in the resin layer from the silicone resin layer to the surface of the thin glass substrate is extremely low. Therefore, after separating the glass substrates, the supporting glass substrate on which the silicone resin layer is formed can be repeatedly used for lamination with other thin glass substrates. In addition, since components in the silicone resin layer are unlikely to migrate to the surface of the thin glass substrate after separation, there is no possibility of poor attachment or the like when a polarizing plate or the like is attached to the surface of the thin glass substrate.

  In order to obtain a silicone resin layer having low silicone migration, a release paper silicone that does not contain a component having high migration may be used. As a general method, a non-reactive silicone may be blended in order to easily release the silicone for release paper. In this case, as the non-reactive silicone, a linear dimethylpolysiloxane having a very high molecular weight or a relatively low molecular weight in which a phenyl group or higher alkyl group is introduced to reduce the compatibility with the cured film is used. It is done. Since such a non-reactive silicone is a component having a high migration property, the release paper silicone used in the present invention preferably has a non-reactive silicone content of 5% by mass or less. It is more preferable that substantially no silicone is contained.

  In the present invention, preferable examples of silicone for release paper include KNS-320A, KS-847 (both manufactured by Shin-Etsu Silicone Co., Ltd.), TPR6700 (manufactured by GE Toshiba Silicone Co., Ltd.), vinyl silicone “8500”. (Arakawa Chemical Industries, Ltd.) and methyl hydrogen polysiloxane “12031” (Arakawa Chemical Industries, Ltd.), vinyl silicone “11364” (Arakawa Chemical Industries, Ltd.) and methyl hydrogen polysiloxane “12031” And a combination of vinyl silicone “11365” and methyl hydrogen polysiloxane “12031”. KNS-320A, KS-847, and TPR6700 are silicones that already contain a main agent and a crosslinking agent.

  The thickness of the easily peelable and non-adhesive silicone resin layer is preferably 1 to 100 μm. When the thickness of the silicone resin layer is less than 1 μm, the thin glass substrate and the silicone resin layer may not be sufficiently adhered. Further, even when foreign matter is present, it tends to lead to a convex defect of the thin glass substrate. On the other hand, if it exceeds 100 μm, the contribution to the properties as a silicone resin layer having easy peelability and non-adhesiveness is no longer significant, and it takes time to cure the silicone resin, which is not economical. The thickness of the silicone resin layer is more preferably 5 to 20 μm. If the thickness of a silicone resin layer is 5-20 micrometers, favorable adhesiveness can be exhibited with respect to the thin glass substrate of a wide thickness.

The method for forming the easily peelable and non-adhesive silicone resin layer on the supporting glass substrate is not particularly limited, and can be appropriately selected from known methods. When silicone for release paper is used for the silicone resin layer, after the silicone for release paper is applied to the surface of the supporting glass substrate, the silicone for release paper is cured before laminating the thin glass.
As a method for coating the release paper silicone, known methods can be used. Specifically, for example, spray coating, die coating, spin coating, dip coating, roll coating, bar coating, and the like. Method, screen printing method, gravure coating method and the like. These coating methods can be appropriately selected according to the type of silicone for release paper.
For example, when the release paper silicone is a solventless type, a die coating method, a spin coating method, and a screen printing method are suitable.
When the silicone for release paper is a solventless type, its coating amount is preferably from ^{1g / m 2 ~100g / m 2} , more preferably ^{5g / m 2 ~20g / m 2} .

In the case of an addition reaction type silicone, a mixture of a release paper silicone containing a main agent and a crosslinking agent and a catalyst is applied onto a supporting glass substrate by any of the methods described above, and then cured by heating. The heat curing conditions vary depending on the blending amount of the catalyst. For example, when 2 parts by mass of a platinum-based catalyst is blended with 100 parts by mass of the release paper silicone, it is 50 ° C. to 250 ° C., preferably 100 ° C. C. to 200.degree. C. for 5 to 60 minutes, preferably 10 to 30 minutes.
In order to obtain a silicone resin layer having low silicone migration, it is preferable to proceed the curing reaction as much as possible so that an unreacted silicone component does not remain in the silicone resin layer. If heat curing is performed under the above-described conditions, unreacted silicone components can be prevented from remaining in the silicone resin layer. Compared to the above conditions, if the heating time is too long or the heating temperature is too high, the silicone resin undergoes oxidative decomposition at the same time, and a low molecular weight silicone component is generated, resulting in high silicone migration. .
In order to improve the peelability after the heat treatment, it is preferable that the curing reaction proceeds as much as possible so that an unreacted silicone component does not remain in the silicone resin layer.

After forming the easily peelable and non-adhesive silicone resin layer on the supporting glass substrate, a thin glass substrate is laminated on the silicone resin forming surface of the supporting glass substrate. When silicone for release paper is used for the silicone resin layer, the release paper silicone coated on the support glass substrate is heated and cured to form a silicone resin layer, and then the thin glass substrate is formed on the silicone resin forming surface of the support glass substrate. Laminate.
By curing the silicone for release paper by heating, the cured silicone resin is chemically bonded to the supporting glass, and the silicone resin layer is bonded to the supporting glass by an anchor effect. By these actions, the silicone resin layer is fixed to the supporting glass substrate.
On the other hand, the thin glass substrate is fixed to the silicone resin layer by the force due to the van der Waals force between the solid molecules facing each other very close, that is, the adhesion force. When the laminated thin glass substrate is separated, the components in the silicone resin layer are prevented from transferring to the surface of the separated thin glass substrate. These effects can be obtained by laminating a thin glass substrate after forming a silicone resin layer on the supporting glass substrate.
In other words, by using the release paper silicone, the supporting glass substrate and the thin glass substrate can be held in a laminated state, and when the thin glass substrate is separated, the silicone is applied to the surface of the thin glass substrate. Migration of the components of the resin layer can also be prevented, and as a result, the object of the present invention can be achieved.

The procedure for laminating the thin glass substrate on the silicone resin-formed surface of the supporting glass substrate can be carried out using a known method, for example, after laminating the thin glass substrate on the silicone resin-formed surface in a normal pressure environment. The laminate may be crimped using a roll or a press. By pressure bonding with a roll or a press, the silicone resin layer and the thin glass substrate are more closely attached.
Moreover, the air bubbles mixed in the silicone resin layer are easily removed by pressure bonding with a roll or a press.
However, it is preferable to employ a vacuum laminating method or a vacuum pressing method from the viewpoint of suppressing the mixing of bubbles and ensuring good adhesion. By laminating under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not easily connected to the convex defects of the thin glass substrate.

When laminating a thin glass substrate on the surface of the supporting glass substrate on which the silicone resin layer is formed, it is necessary to sufficiently clean the surface of the thin glass substrate and laminate in a clean environment.
If it is a very small foreign matter, the flexible silicone resin layer is deformed and absorbed by the silicone resin layer, and does not affect the flatness of the thin glass substrate surface after lamination, but the amount and size This is because there is a possibility that it may lead to a convex defect on the surface of the thin glass substrate after lamination.

  Next, a method for manufacturing the display device of the present invention will be described. In the manufacturing method of the display device of the present invention, after the thin glass laminate of the present invention is formed by the above procedure, a predetermined process for manufacturing the display device is performed on the thin glass substrate of the laminate. In this specification, the term “predetermined process for manufacturing a display device” includes a wide variety of processes performed in the manufacturing process when manufacturing a display device such as an LCD or an OLED. As a specific example of the processing performed here, in the case of manufacturing an LCD, for example, a process of forming an array on a thin glass substrate, a color filter is formed on a thin glass substrate different from the thin glass substrate And various processes such as a process of laminating a thin glass substrate on which an array is formed and a thin glass substrate on which a color filter is formed (array / color filter laminating process). Specific examples of the treatment include pure water cleaning, drying, film formation, resist coating, exposure, development, etching, and resist removal. Furthermore, as a process performed after implementing an array color filter bonding process, there exists a liquid-crystal injection | pouring process and the sealing process of the injection port performed after implementation of this process, The process performed by these processes is also included. However, it is not necessary to perform all of these processes in the state of a laminated body. For example, from the viewpoint of strength and handleability, it is possible to carry out the liquid crystal injection process after separating the thin glass substrate and the supporting glass substrate after performing the array / color filter bonding step in the state of a laminate. preferable.

  In the method for manufacturing a display device of the present invention, both the glass substrate forming the array and the glass substrate forming the color filter may not be a thin glass substrate. For example, a thin glass substrate on which an array is formed and a glass substrate with a normal thickness on which a color filter is formed may be bonded together, or a glass substrate with a normal thickness on which an array is formed and a color filter. You may paste together the formed thin glass substrate. In these cases, the total thickness of the display element after being formed into cells becomes thick, but there is an advantage that the mechanical strength can be improved. The normal thickness glass substrate here means a glass substrate having a thickness of 0.3 mm or more.

  Taking the case of manufacturing an OLED as an example, as a process for forming an organic EL structure on a thin glass substrate, a process of forming a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport Various processes such as a process for depositing layers and the like, a sealing process, and the like, and specific examples of the processes performed in these processes include a film forming process, a vapor deposition process, and a sealing plate bonding process. .

  After performing the said predetermined process, a thin glass substrate and a support glass substrate are isolate | separated. Separation can be carried out by manual peeling, but it can be more easily peeled off by giving an edge to the edge with a razor blade or by injecting air into the lamination interface. Since the peeled supporting glass substrate is in a state in which a silicone resin layer having easy peelability and non-adhesiveness is still formed, it can be used again for lamination with another thin glass substrate. In addition, if the silicone resin layer has low silicone migration, the silicone resin layer after separation has a high residual adhesion rate. It can be used repeatedly for lamination with a glass substrate.

  After separating the thin glass substrate and the supporting glass substrate, a display device having the thin glass substrate is obtained through a desired process. In the case of LCD, for example, the steps performed here are a step of dividing into cells of a desired size, a step of injecting liquid crystal and then sealing the injection port, a step of attaching a polarizing plate, a step of forming a module Is mentioned. In the case of an OLED, in addition to these steps, a step of assembling a thin glass substrate on which an organic EL structure is formed and a counter substrate is included. Note that the step of dividing into cells of a desired size is preferably cut by a laser cutter because the strength of the thin glass substrate is not lowered by the cutting process and no cullet is produced.

  The present invention also provides a release paper silicone for a thin glass laminate described above, which is used for laminating a supporting glass substrate and a thin glass substrate.

Example 1
A support glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 400 mm, a width of 300 mm, a thickness of 0.7 mm, and a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C. is cleaned by pure water cleaning, UV cleaning, etc. A spin coater was prepared by mixing a solvent-free addition reaction type release paper silicone (KNS-320A manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts by mass and a platinum catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) 2 parts by mass on a substrate. (Coating amount: 10 g / m ² ) and cured by heating at 180 ° C. for 30 minutes in the air to obtain a silicone resin layer having a film thickness of 16 μm.
Clean the surface of the thin glass substrate (AN100) with a length of 400 mm, width of 300 mm, thickness of 0.1 mm, and linear expansion coefficient of 38 × 10 ⁻⁷ / ° C. with pure water cleaning, UV cleaning, etc. After that, the silicone resin layer-forming surface of the supporting glass and the thin glass substrate are bonded together by a vacuum press at room temperature, and the thin glass laminate having the silicone resin layer having easy peelability and non-adhesiveness of the present invention ( A thin glass laminate A) was obtained.
In the thin glass laminate A, the thin glass substrate was in close contact with the silicone resin layer without generating bubbles, had no convex defects, and had good smoothness.
The formed thin glass laminate A was evaluated as follows.
(1) Simple peeling test The thin glass laminated body A was installed so that the thin glass substrate might become an upper side, and the support glass substrate was fixed using the jig | tool. In this state, a part of the peripheral portion of the thin glass substrate was peeled off from the support glass substrate with a razor, and when the thin glass substrate was further separated from the support glass substrate by hand, the thin glass substrate could be easily peeled off.
Moreover, although the said peeling test was implemented also about the thin glass laminated body A after heat-processing in the air | atmosphere for 300 degreeC for 1 hour, it can peel from a support glass substrate, without destroying a thin glass substrate, and is heat resistant. Was also good.
(2) Peel test (1) (before heating)
The test was carried out using a jig as shown in FIG.
The thin glass laminate A is cut into a size of 50 mm long × 50 mm wide, and the glass (supporting glass substrate 40 and thin glass substrate 50) on both sides of the thin glass laminated body A is 50 mm long × 50 mm wide × 5 mm thick. The polycarbonates 20 were bonded together with an epoxy two-component glass adhesive. Further, polycarbonate 25 having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm was further vertically bonded to the surfaces of both the bonded polycarbonates 20. As shown in FIG. 2, the location where the polycarbonate 25 is pasted is the position where the vertical direction is the end of the polycarbonate 20 and the horizontal direction is parallel to the side of the polycarbonate 20.
The thin glass laminate A in which the polycarbonates 20 and 25 were bonded together was placed so that the supporting glass substrate was on the lower side. When the polycarbonate 25 affixed to the thin glass substrate side is fixed with a jig, and the polycarbonate 25 affixed to the support glass substrate side is pulled vertically downward at a speed of 300 mm / min, a load of 13.8 kg (0. The supporting glass substrate peeled off when 55 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate.
(3) Peel test (1) (after heating)
Peel test (1) (heating), except that the thin glass laminate A after the lamination was heated in the atmosphere at 300 ° C. for 1 hour instead of using the thin glass laminate A in the peel test (1) (before heating) The peel test (1) (after heating) was carried out in the same manner as before. The support glass substrate peeled off when a load of 45 kg weight (1.8 kg weight / cm ² ) was applied. No cracks or the like occurred in the supporting glass substrate or the thin glass substrate.
(4) Shear strength test The test was implemented using the jig | tool like FIG.
The thin glass laminate A is cut into a size of 25 mm long × 25 mm wide, and the glass (supporting glass substrate 40 and thin glass substrate 50) on both sides of the thin glass laminated body A is 25 mm long × 50 mm wide × 3 mm thick. The polycarbonate 30 was bonded with an adhesive for epoxy two-component glass. As shown in FIG. 3, the area of the bonding location was 25 mm long × 25 mm wide. Further, as shown in FIG. 3, the pasting locations were the lower surface portion of the supporting glass substrate and the right half portion of the polycarbonate 30, and the upper surface portion of the thin glass substrate and the left half portion of the polycarbonate 30.
The polycarbonate 30 bonded to the thin glass substrate was fixed with a jig, and the polycarbonate 30 bonded to the supporting glass substrate was pulled in the lateral direction in FIG. 3 (the length direction of the polycarbonate 30) at a pulling speed of 0.5 mm / min. . The supporting glass substrate peeled off when a load of 13 kg weight (2.1 kg weight / cm ² ) was applied. No cracks or the like occurred in the supporting glass substrate or the thin glass substrate. In addition, the thin glass laminated body A after baking was the same value as before baking.
(5) Residual adhesion rate measurement Using the measurement method described in [0032], the residual adhesion rate of the silicone resin layer of the thin glass laminate A was measured, and the residual adhesion rate was 106%.

(Example 2)
Instead of a mixture of 100 parts by mass of silicone for solvent-free addition reaction type release paper (KNS-320A manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 parts by mass of platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.), Linear polyorganosiloxane having a vinyl group (“8500” manufactured by Arakawa Chemical Industries, Ltd.), methyl hydrogen polysiloxane having a hydrosilyl group in the molecule (“12031” manufactured by Arakawa Chemical Industries, Ltd.), and a platinum-based catalyst (The thin glass laminated body B of this invention) was processed like Example 1 except the point which used the mixture with (Arakawa Chemical Industries Ltd. "CAT12070"). Here, the mixing ratio of the linear polyorganosiloxane and the methylhydrogen polysiloxane was adjusted so that the molar ratio of hydrosilyl group to vinyl group was 1.5 / 1. The platinum-based catalyst was added in an amount of 5 parts by mass with respect to a total of 100 parts by mass of the linear polyorganosiloxane and methyl hydrogen polysiloxane.
In the thin glass laminate B, the thin glass substrate was in close contact with the silicone resin layer without generating bubbles, and had no convex defects and good smoothness.
The formed thin glass laminate B was evaluated as follows.
(1) Simple peeling test As in Example 1, the thin glass laminate B was placed so that the thin glass substrate was on the upper side, and the supporting glass substrate was fixed using a jig. In this state, a part of the peripheral portion of the thin glass substrate was peeled off from the support glass substrate with a razor, and when the thin glass substrate was further separated from the support glass substrate by hand, the thin glass substrate could be easily peeled off.
Moreover, although the said peeling test was implemented also about the thin glass laminated body B after heat-processing in air | atmosphere for 1 hour at 300 degreeC, it can peel from a support glass substrate, without destroying a thin glass substrate, and is heat resistant. Was also good.
(2) Peel test (1) (before heating)
Peel test (1) (before heating) in the same manner as the peel test (1) (before heating) of Example 1 except that the thin glass laminate B is used instead of using the thin glass laminate A in Example 1. Carried out. When a load of 9 kg weight (0.36 kg weight / cm ² ) was applied, the supporting glass substrate was peeled off. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate.
(3) Peel test (1) (after heating)
Instead of using the thin glass laminate A in Example 1, the peel test (1) (after heating) was performed in the same manner as the peel test (1) (after heating) in Example 1 except that the thin glass laminate B was used. Carried out. The supporting glass substrate peeled off when a load of 15 kg weight (0.61 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate.
(4) Shear strength test A shear strength test was performed in the same manner as the shear strength test of Example 1 except that the thin glass laminate B was used instead of the thin glass laminate A in Example 1. The supporting glass substrate peeled off when a 9 kg load (1.4 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate. In addition, the thin glass laminated body B after baking was the same value as before baking.
(5) Residual adhesion rate measurement Using the measurement method described in Example 1, the residual adhesion rate of the silicone resin layer of the thin glass laminate B was measured, and the residual adhesion rate was 108%.

(Example 3)
In Example 2, except that the mixing ratio of linear polyorganosiloxane and methylhydrogenpolysiloxane was adjusted so that the molar ratio of hydrosilyl group to vinyl group was 1.0 / 1. In the same manner as in No. 2, a thin glass laminate (thin glass laminate C) was obtained.
In the thin glass laminate C, the thin glass substrate was in close contact with the silicone resin layer without generating bubbles, had no convex defects, and had good smoothness.
The formed thin glass laminate C was evaluated as follows.
(1) Simple peel test The thin glass laminate C was placed so that the thin glass substrate was on the upper side, and the support glass substrate was fixed using a jig. In this state, a part of the peripheral portion of the thin glass substrate was peeled off from the support glass substrate with a razor, and when the thin glass substrate was further separated from the support glass substrate by hand, the thin glass substrate could be easily peeled off.
In addition, for the thin glass laminate C after heat treatment in the atmosphere at 300 ° C. for 1 hour, the above peel test was carried out, but it can be easily peeled off from the supporting glass substrate without destroying the thin glass substrate, The heat resistance was also good.
(2) Peel test (1) (before heating)
Peel test (1) (before heating) in the same manner as the peel test (1) (before heating) of Example 1 except that the thin glass laminate C is used instead of using the thin glass laminate A in Example 1. Carried out. The supporting glass substrate peeled off when a load of 12 kg weight (0.47 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate.
(3) Peel test (1) (after heating)
Peel test (1) (after heating) in the same manner as the peel test (1) (after heating) of Example 1 except that the thin glass laminate C is used instead of using the thin glass laminate A in Example 1. Carried out. The supporting glass substrate peeled off when a load of 12 kg weight (0.47 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate.
(4) Shear strength test A shear strength test was conducted in the same manner as the shear strength test of Example 1 except that the thin glass laminate C was used instead of the thin glass laminate A in Example 1. The supporting glass substrate peeled off when a load of 12 kg weight (1.9 kg weight / cm ² ) was applied. No cracking or the like occurred in the supporting glass substrate or the thin glass substrate. In addition, the thin glass laminated body C after baking was the same value as before baking.
(5) Residual adhesion rate measurement Using the measurement method described in Example 1, the residual adhesion rate of the silicone resin layer of the thin glass laminate C was measured, and the residual adhesion rate was 105%.
(Example 4)
Solvent-free addition reaction type release paper silicone (KNS-320A manufactured by Shin-Etsu Silicone Co., Ltd.) instead of solvent-free addition reaction type release paper silicone (KS-847 manufactured by Shin-Etsu Silicone Co., Ltd.) The thin glass laminate of the present invention was carried out in the same manner as in Example 1 except that a platinum catalyst (CAT-PL-50T manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of CAT-PL-56 manufactured by the company. A body (thin glass laminate D) was obtained.
In the thin glass laminate D, the thin glass substrate was in close contact with the silicone resin layer without generating bubbles, had no convex defects, and had good smoothness.
When the simple peeling test was implemented about the thin glass laminated body D, the thin glass substrate was able to be peeled easily. Moreover, although the simple peeling test was implemented also about the thin glass laminated body D after heat-processing in the air | atmosphere for 300 degreeC for 1 hour, the thin glass substrate could be peeled easily and heat resistance was also favorable.
As in Example 1, when the residual adhesion rate of the silicone resin layer formed by the above procedure was measured, the residual adhesion rate was 101%.

(Example 5)
In this example, an LCD is manufactured using the thin glass laminate A obtained in Example 1. Two thin glass laminates A are prepared, and an array is formed on one sheet to form an array on the surface of the thin glass substrate. The remaining one sheet is subjected to a color filter forming step to form a color filter on the surface of the thin glass substrate. After laminating the thin glass substrate on which the array is formed and the thin glass substrate on which the color filter is formed, an edge is given to the end with a razor blade to separate the supporting glass substrate. Subsequently, the thin glass substrate is cut using a laser cutter and divided into 28 cells of 51 mm in length × 38 mm in width, and then a liquid crystal injection step and an injection port sealing step are performed to form a liquid crystal cell. A step of attaching a polarizing plate to the formed liquid crystal cell is performed, and then a module formation step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

(Example 6)
In this example, an LCD is manufactured using the thin glass laminate A obtained in Example 1 and a non-alkali glass substrate having a thickness of 0.7 mm. A thin glass laminate A is prepared, and a color filter forming step is performed to form a color filter on the surface of the thin glass substrate. On the other hand, an array formation process is performed on a non-alkali glass substrate (Asahi Glass Co., Ltd. AN-100) having a thickness of 0.7 mm to form an array on the surface of the non-alkali glass substrate having a thickness of 0.7 mm.
After laminating the thin glass substrate laminate on which the color filter is formed and the non-alkali glass substrate having a thickness of 0.7 mm on which the array is formed, the edge is peeled off at the end with a razor blade, and the thin glass A supporting glass substrate is separated from the laminate. Subsequently, the thin glass substrate-non-alkali glass substrate bonded body is divided into 28 cells measuring 51 mm long by 38 mm wide. At this time, the thin glass substrate is cut with a laser cutter. On the other hand, the alkali-free glass substrate is cut using a laser cutter or a scribe-break method.
Thereafter, a liquid crystal injection step and an injection port sealing step are performed to form a liquid crystal cell. A step of attaching a polarizing plate to the formed liquid crystal cell is performed, and then a module formation step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

(Example 7)
In this example, an LCD is manufactured using the thin glass laminate B obtained in Example 2. Two sheet glass laminates B are prepared, and an array is formed on one sheet to form an array on the surface of the sheet glass substrate. The remaining one sheet is subjected to a color filter forming step to form a color filter on the surface of the thin glass substrate. After laminating the thin glass substrate on which the array is formed and the thin glass substrate on which the color filter is formed, an edge is given to the end with a razor blade to separate the supporting glass substrate. Subsequently, the thin glass substrate is cut using a laser cutter and divided into 28 cells of 51 mm in length × 38 mm in width, and then a liquid crystal injection step and an injection port sealing step are performed to form a liquid crystal cell. A step of attaching a polarizing plate to the formed liquid crystal cell is performed, and then a module formation step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

(Example 8)
In this example, an OLED is manufactured using the thin glass laminate D obtained in Example 4. A process for forming a transparent electrode, a process for forming an auxiliary electrode, a process for depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like, and a process for sealing them are performed to obtain a thin glass laminate D An organic EL structure is formed on the thin glass substrate. Next, the supporting glass substrate is separated. Subsequently, the thin glass substrate is cut using a laser cutter and divided into 40 cells of 41 mm length × 30 mm width, and then the thin glass substrate on which the organic EL structure is formed and the counter substrate are assembled, and the module is assembled. A formation process is performed to produce an OLED. There is no problem in characteristics of the OLED obtained in this way.

(Comparative Example 1)
Except that a silicone resin (SH805 manufactured by Toray Dow Corning Co., Ltd.) was applied on a support glass substrate with a spin coater and heat cured at 250 ° C. for 1 hour to obtain a silicone resin layer having a film thickness of 16 μm. The same procedure as in Example 1 was performed to obtain a thin glass laminate E of Comparative Example.
In the thin glass laminate E, the silicone resin layer and the supporting glass substrate were not sufficiently adhered, and the laminate was not constituted.

(Comparative Example 2)
A silicone pressure-sensitive adhesive (YR3340 manufactured by GE Toshiba Silicone Co., Ltd.) was applied on a supporting glass substrate with a spin coater, and heat cured at 150 ° C. for 10 minutes in the air to obtain a silicone resin layer having a film thickness of 16 μm. Except for the above, the same procedure as in Example 1 was performed to obtain a thin glass laminate F of Comparative Example.
In the thin glass laminate F, the thin glass substrate was sufficiently adhered to the silicone resin layer and had good smoothness, but air bubbles were mixed in the silicone resin layer, and the mixed air bubbles were removed. I could not.
When the simple peeling test was implemented about the thin glass laminated body F, it was difficult to peel a thin glass substrate.
Moreover, about the thin glass laminated body F, when a peeling test (1) (before heating), a peeling test (1) (after heating), and a shear strength test were conducted like Example 1, a support glass substrate and a thin glass substrate were carried out. Was not peeled off, and peeling occurred at the interface between the polycarbonate and the glass substrate. Therefore, the supporting glass substrate and the thin glass substrate could not be peeled off.

The thin glass laminate obtained by the present invention can be used as a glass substrate for various display devices.

It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2005-230434 filed on August 9, 2005 are cited here as disclosure of the specification of the present invention. Incorporated.

Claims (23)

  A thin glass laminate obtained by laminating a thin glass substrate and a supporting glass substrate, wherein the thin glass substrate and the supporting glass substrate are interposed through a silicone resin layer having easy peelability and non-adhesiveness. A thin glass laminate characterized by being laminated.   The thin glass laminate according to claim 1, wherein the easily peelable and non-adhesive silicone resin layer further has low silicone migration.   The thin glass laminate according to claim 1 or 2, wherein the easily peelable and non-adhesive silicone resin layer is a layer made of a cured product of silicone for release paper.   The cured product of the release paper silicone is a cross-linked reaction product of a linear polyorganosiloxane having vinyl groups at both ends and / or side chains and a methylhydrogen polysiloxane having a hydrosilyl group in the molecule. A thin glass laminate according to claim 3.   In the mixing ratio of the linear polyorganosiloxane and the methyl hydrogen polysiloxane, the mixing ratio is adjusted so that the molar ratio of hydrosilyl group to vinyl group is 1.3 / 1 to 0.7 / 1. The thin glass laminated body of Claim 4 to adjust.   The thin glass according to any one of claims 1 to 5, wherein a thickness of the thin glass substrate is less than 0.3 mm, and a total thickness of the supporting glass substrate and the silicone resin layer is 0.5 mm or more. Laminated body. The thin glass laminate according to any one of claims 1 to 6, wherein a difference between a linear expansion coefficient of the supporting glass substrate and a linear expansion coefficient of the thin glass substrate is 15 × 10 ^-7 / ° C or less. The thin glass laminate according to claim 1, wherein the silicone resin layer has a surface energy of 16 to 21 erg / cm ² . A thin glass laminate formed by laminating a thin glass substrate and a supporting glass substrate, wherein the thin glass substrate and the supporting glass substrate are laminated via a silicone resin layer, and the silicone resin A thin glass laminate having a shearing force of 0.1 kg / cm ² or more and a peeling force of 2 kg / cm ² or less. Forming a silicone resin layer having easy peelability and non-adhesiveness on a supporting glass substrate;
Laminating a thin glass substrate on the silicone resin layer forming surface of the support glass, and forming a thin glass laminate,
Performing a predetermined process for manufacturing a display device on the thin glass substrate;
And a step of separating the processed thin glass substrate and the supporting glass substrate. A method for manufacturing a display device using a thin glass laminate, comprising:   The method for producing a display device using the thin glass laminate according to claim 10, wherein the easily peelable and non-adhesive silicone resin layer further has low silicone migration. Forming a silicone resin layer comprising a cured product of silicone for release paper on a supporting glass substrate;
Laminating a thin glass substrate on the silicone resin layer forming surface of the support glass, and forming a thin glass laminate,
Performing a predetermined process for manufacturing a display device on the thin glass substrate;
The manufacturing method of the display apparatus using the thin glass laminated body of Claim 10 or 11 including the process of isolate | separating the processed said thin glass substrate and the said support glass substrate.   The step of forming a silicone resin layer composed of a cured product of silicone for release paper on a support glass substrate includes coating silicone for release paper on the support glass substrate and then curing the silicone for release paper. A method for manufacturing a display device using the thin glass laminate according to claim 12.   The silicone for release paper includes linear polyorganosiloxane having vinyl groups at both ends and / or side chains, methylhydrogen polysiloxane having hydrosilyl groups in the molecule, and a platinum-based catalyst. Or the manufacturing method of the display apparatus using the thin glass laminated body of 13.   The mixing ratio of the linear polyorganosiloxane and the methyl hydrogen polysiloxane is adjusted so that the molar ratio of hydrosilyl group to vinyl group is 1.3 / 1 to 0.7 / 1. The manufacturing method of the display apparatus using the thin glass laminated body of Claim 14.   The method for producing a display device using a thin glass laminate according to any one of claims 12 to 15, wherein the silicone for release paper has a content of non-reactive silicone of 5% by mass or less.   The method for producing a display device using a thin glass laminate according to any one of claims 12 to 16, wherein the silicone for release paper is applied using a die coating method, a spin coating method, or a screen printing method.   The manufacturing method of the display apparatus using the thin glass laminated body in any one of Claim 12 thru | or 17 which heat-hardens the said silicone for release paper at the temperature of 50-250 degreeC.   19. The step of laminating a thin glass substrate on the silicone resin layer forming surface of the supporting glass substrate to form a thin glass laminate is performed using a vacuum press or a vacuum laminate. A method for manufacturing a display device using a thin glass laminate.   20. The thin glass according to claim 10, wherein a thickness of the thin glass substrate is less than 0.3 mm, and a total thickness of the support glass substrate and the silicone resin layer is 0.5 mm or more. A method for manufacturing a display device using a laminate. The difference between the linear expansion coefficient of the supporting glass substrate and the linear expansion coefficient of the thin glass substrate is 15 × 10 ^-7 / ° C or less, and the thin glass laminate according to any one of claims 10 to 20 is used. Manufacturing method of the display device.   A linear polyorganosiloxane having a vinyl group at both ends and / or side chains, and a crosslinking agent comprising a methylhydrogenpolysiloxane having a hydrosilyl group in the molecule; A thin plate characterized in that the mixing ratio of organosiloxane and methylhydrogenpolysiloxane is adjusted so that the molar ratio of hydrosilyl group to vinyl group is 1.3 / 1 to 0.7 / 1 Silicone for release paper for glass laminates.   The silicone for release paper for thin glass laminates according to claim 22, wherein the content of non-reactive silicone is 5% by mass or less.

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